Steric and electronic effects influencing β-aryl elimination in the Pd ...
Steric and electronic effects influencing β-aryl elimination in the Pd-catalyzed carbon-carbon single bond activation of triarylmethanols
James R. Bour, Jacob C. Green, Valerie J. Winton, Jeffrey B. Johnson* Department of Chemistry, Hope College, Holland, MI 49423 [email protected]
Supporting Information
Results from Competition Experiments Using Two Aryl Bromides
S2
Plot of Cleavage Ratio versus Electronic Effects
S2
Representative GC/MS Results
S3
1
S5
H, 13C and 19F NMR Spectra of New Compounds
Table S1. Results from Aryl Bromide Competition Reactions Entrya 1 2 3 4 5 6d
R-Br R’-Br 4-CF3-C6H4 C6H5 4-MeO-C6H4 C6H5 4-CF3-C6H4 4-MeO-C6H4 3,5-(CF3)2-C6H3 4-CF3-C6H4 4-CF3-C6H4 2-MeO-C6H4 4-MeO-C6H4 3-MeO-C6H4 2-MeO-C6H4
Combined Conversion (%)b 55 95 72 81 84 72
Ratio (R:R’)c >50 : 1 1 : 1.2 >50 : 1 5.2 : 1 7.4 : 1 1 : 10 : 3
a
Reactions performed in refluxing o-xylene with [Ph3COH] = 0.167 M, [R-Br] = 0.20 M, [R’-Br] = 0.20 [Pd(OAc)2] = 8.3 mM, [PPh3] = 0.043 M, [CsCO3] = 0.22 M for 16 h. b Total amount of triphenylmethanol converted to products. c Determined by GC/MS analysis. Values are the average of three experiments. d Run in the presence of three aryl bromides, each at 0.20 M.
Scheme S1. Plot of Migratory Aptitude of Aryl Groups Relative to Unsubstituted Phenyl Ring Versus Sigma Valuea O Pd(OAc)2 (5 mol%) + Ph Ar OH Ph 2 Ph PPh3 (25 mol%) 5 + Ph Br Ph o-xylene, reflux Ar O Ph + Ph Ph Cs2CO3, 16 h 4 Ar Ph 3 6
a) Plot constructed from data in Tables 1 and 2 of manuscript. The data point labels refer to substitution of aryl ring in aryldiphenylmethanol substrates.
S2
Representative GC/MS Results Figure S1. GC/MS Chromatogram from reaction of substrate 4c with bromobenzene under standard reaction conditions.
Figure S2. GC/MS Chromatogram from reaction of substrate 4g with bromobenzene under standard reaction conditions.
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Figure S3. GC/MS Chromatogram from reaction of substrate 4j with bromobenzene under standard reaction conditions.
Figure S4. GC/MS Chromatogram from reaction of substrate 4o with bromobenzene under standard reaction conditions.
S4
Figure S5. (2,5-difluorophenyl)diphenylmethanol (4p) – 1H NMR
Figure S6. (2,5-difluorophenyl)diphenylmethanol (4p) – 13C NMR
S6
Figure S7. (2,5-difluorophenyl)diphenylmethanol (4p) – 19F NMR
S7
Figure S8. (3,4-difluorophenyl)diphenylmethanol (4q) – 1H NMR
S8
Figure S9. (3,4-difluorophenyl)diphenylmethanol (4q) – 13C NMR
S9
Figure S10. (3,4-difluorophenyl)diphenylmethanol (4q) – 19F NMR
S10
Figure S11. (2,6-difluorophenyl)diphenylmethanol (4r) – 1H NMR
S11
Figure S12. (2,6-difluorophenyl)diphenylmethanol (4r) – 13C NMR
S12
Figure S13. (2,6-difluorophenyl)diphenylmethanol (4r) – 19F NMR
S13
Figure S14. (3,5-difluorophenyl)diphenylmethanol (4s) – 1H NMR
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Figure S15. (3,5-difluorophenyl)diphenylmethanol (4s) – 13C NMR
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Figure S16. (3,5-difluorophenyl)diphenylmethanol (4s) – 19F NMR
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Figure S17. (3,4,5-trifluorophenyl)diphenylmethanol (4t) – 1H NMR
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Figure S18. (3,4,5-trifluorophenyl)diphenylmethanol (4t) – 13C NMR
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Figure S19. (3,4,5-trifluorophenyl)diphenylmethanol (4t) – 19F NMR
S19
James R. Bour, Jacob C. Green, Valerie J. Winton, Jeffrey B. Johnson* Department of Chemistry, Hope College, Holland, MI 49423 [email protected]
Supporting Information
Results from Competition Experiments Using Two Aryl Bromides
S2
Plot of Cleavage Ratio versus Electronic Effects
S2
Representative GC/MS Results
S3
1
S5
H, 13C and 19F NMR Spectra of New Compounds
Table S1. Results from Aryl Bromide Competition Reactions Entrya 1 2 3 4 5 6d
R-Br R’-Br 4-CF3-C6H4 C6H5 4-MeO-C6H4 C6H5 4-CF3-C6H4 4-MeO-C6H4 3,5-(CF3)2-C6H3 4-CF3-C6H4 4-CF3-C6H4 2-MeO-C6H4 4-MeO-C6H4 3-MeO-C6H4 2-MeO-C6H4
Combined Conversion (%)b 55 95 72 81 84 72
Ratio (R:R’)c >50 : 1 1 : 1.2 >50 : 1 5.2 : 1 7.4 : 1 1 : 10 : 3
a
Reactions performed in refluxing o-xylene with [Ph3COH] = 0.167 M, [R-Br] = 0.20 M, [R’-Br] = 0.20 [Pd(OAc)2] = 8.3 mM, [PPh3] = 0.043 M, [CsCO3] = 0.22 M for 16 h. b Total amount of triphenylmethanol converted to products. c Determined by GC/MS analysis. Values are the average of three experiments. d Run in the presence of three aryl bromides, each at 0.20 M.
Scheme S1. Plot of Migratory Aptitude of Aryl Groups Relative to Unsubstituted Phenyl Ring Versus Sigma Valuea O Pd(OAc)2 (5 mol%) + Ph Ar OH Ph 2 Ph PPh3 (25 mol%) 5 + Ph Br Ph o-xylene, reflux Ar O Ph + Ph Ph Cs2CO3, 16 h 4 Ar Ph 3 6
a) Plot constructed from data in Tables 1 and 2 of manuscript. The data point labels refer to substitution of aryl ring in aryldiphenylmethanol substrates.
S2
Representative GC/MS Results Figure S1. GC/MS Chromatogram from reaction of substrate 4c with bromobenzene under standard reaction conditions.
Figure S2. GC/MS Chromatogram from reaction of substrate 4g with bromobenzene under standard reaction conditions.
S3
Figure S3. GC/MS Chromatogram from reaction of substrate 4j with bromobenzene under standard reaction conditions.
Figure S4. GC/MS Chromatogram from reaction of substrate 4o with bromobenzene under standard reaction conditions.
S4
Figure S5. (2,5-difluorophenyl)diphenylmethanol (4p) – 1H NMR
Figure S6. (2,5-difluorophenyl)diphenylmethanol (4p) – 13C NMR
S6
Figure S7. (2,5-difluorophenyl)diphenylmethanol (4p) – 19F NMR
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Figure S8. (3,4-difluorophenyl)diphenylmethanol (4q) – 1H NMR
S8
Figure S9. (3,4-difluorophenyl)diphenylmethanol (4q) – 13C NMR
S9
Figure S10. (3,4-difluorophenyl)diphenylmethanol (4q) – 19F NMR
S10
Figure S11. (2,6-difluorophenyl)diphenylmethanol (4r) – 1H NMR
S11
Figure S12. (2,6-difluorophenyl)diphenylmethanol (4r) – 13C NMR
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Figure S13. (2,6-difluorophenyl)diphenylmethanol (4r) – 19F NMR
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Figure S14. (3,5-difluorophenyl)diphenylmethanol (4s) – 1H NMR
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Figure S15. (3,5-difluorophenyl)diphenylmethanol (4s) – 13C NMR
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Figure S16. (3,5-difluorophenyl)diphenylmethanol (4s) – 19F NMR
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Figure S17. (3,4,5-trifluorophenyl)diphenylmethanol (4t) – 1H NMR
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Figure S18. (3,4,5-trifluorophenyl)diphenylmethanol (4t) – 13C NMR
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Figure S19. (3,4,5-trifluorophenyl)diphenylmethanol (4t) – 19F NMR
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